Production of organic fluorine compounds



Patented Nov. 2, 1948 2,452,975

raonuorron OF ORGANIC FLUORINE COMPOUNDS a William Basil Whalley, Liverpool, England, assigner to Imperial Chemical Industries. Lim

ited, a corporation of GreatBritai'n.

No Drawing Application January 22, 1947,

p Serial No. 723,676

9 Claims. (01. 2e0 e5s) I I z This. invention relates. to the production of denedichloride; Thereaction is suitably-.carriedt: fluoro derivatives of saturated aliphatic hydroout inqan autoclave constructed of a metal reacarbons and more particularly to the production sonably resistant to attack by thereactants, such ofmonofluoro derivatives of such compounds. as mild steel.

The method of fluorinating aliphatic halo- 5 Theprocess may be carried out under widely" hydrocarbons with hydrogen fluoride in the varied conditions-oi temperature and: pressure, presence of a catalyst. consisting of an. antimony Superatmospheric pressure is preferably: emhalide such as antimony pentachloride or an ployed', suitable pressures being ior exampla-(of: antimony fluorochloride is well known. other the order of 100 to 200 lbs. persqhin,v althoughp catalysts have, also beenused for these reactions, lower or higher pressures may beusedif desired for example in U. S. Patents Nos. 2,005,707, and Elevated: temperatures are also. preferable,v for;

2,005,711 .theuse, of metallic halides, inparticular example temperatures Within the range of 50 C. heavy metal halides, for this purposeis described. to 100 C. are suit althflugh W 0 h h Difiiculties have been experienced in attempttemperaturesmaybe used-if desired,

ing toprepare the monofluoro derivatives of some The process may becarried out either batchaliphatic haiohydrocarbons, containing more wise or bya CO 1ti1'1110uS method- In order 1tothan, one atom of halogen. other than fluorin minimise the formationqof the difluoro compound,

attached to. the same terminal carbon atom by such as l,.1-difiuor0ethane, whi h i prod c fiuorination, with hydrogen. fluoridein th presby fluorination of ethylidene dichloride, it is, de-

ence of theusual antimony halide catalysts, the s ra le to remo the m or p nd from tendency being to. produce the difiuoro derivathe, reaction. vessel continuously as it is formed.

tives almost exclusively by this method, together This is, most conveniently effected y p oy n 1 with varying, quantities of. coke.

a continuous process, thewhydrogent fluoride be According to the present invention a process ing fedlcontinuously intothe reaction vessellwhile for the production ota monofluoro derivative of the mOHOfiHOTO Compound is t aw The a saturated halohydrocarbon comprises reacting p p ti o m ofiuor de obtained by the con a saturated aliphatic halogenated hydrocarbon tinuo s e fld isgenemlly her thanthat pr containing at least two atoms of halogen other duced by abatch p oc ss.

thanfluorine attached to, the same terminal car- The following. exa p ate b t oj 0 bon atom. at a temperature of at least (land 30 limit theal'nvention aILParts-being by Weight? at elevated pressure with, anhydrous hydrogen fluoride in. the presence of stannic chloride as l Example 1 catalyst. 495 parts of ethylidene dichloride; 2410 parts of Stannic chloride appears to have a milderacanhydrous hydrogen fluoride and 104 parts of i n as a fl r o y t th n ha o n anhydrous. stannic chloride were charged into a mony pentachlo-ride and the other common antimild steel' autoclave. Themixture was heated to mony halideatalysts. Thus, Whenstannic. chlo- 70 0;, a. gauge pressure oil-110 lbs/sq. in, being ride is used as the catalyst, for example in the maintained. After one hour the evolution of fluorination of ethylidene dichloride with anhyhydrogen chloridehad ceased, and the heating :drous hydrogen fluoride, at least 50% :of the fluo- 40 was thereforestoppedjthe pressure was released rinated product obtained consistsof monofluoride, and the reaction mixture allowed tobool. Disthe yield of difiuoride being correspondingly retillationof the product gave 40% yields, based on duced, and only traces of coke being formed. the ethylidene dichloride used, ofeach-of l-fiuoro- In one form of the invention l fiuoro-l-chlorol-cl'lloroethanean-d Ll-difiuoroethana ethane is prepared by heating ethylidene dichloride with anhydrous hydrogen fluoride in the Example Presence. of stannic chloridii amount of Inla continuousofluorination of ethylidene diydrogen fluoride used should be at least the chloride, 382 parts of ethylidene dichloride and. sto1ch1ometr1c equivalent of the ethylidene d1- 390parts of anhydrous t nnie chloride were chloride used, and it is prcfe a l e a excess charged into a mild steel autoclave and the mix of hyd ogen fluoride. The amount of stannic ture heated to 70 C. When the pressure reached chl e eq 'edls at.least 2. by- We t of the 40 lbs/sq. in., 275 parts of anhydrous hydrogen,

et y e e dichloride u and considerably fluoride ata constant rate of .126 parts per hour.

larger proportions of the. catalyst maybe used werepassed in. The, pressure. of the reaction with advantage. For example, good results are mixture was maintained constant by continuobtained when using amounts of stannic chloride ously taking 01? the fiuorinated product.

rangingfrom 20% to 40% by weight of ethyli- A yield of l-fluoro-l-chloroethane and 1, 1-

3 difluoroethane, based on ethylidene chloride consumed, of 43% and 20% respectively was obtained.

Example 3 In a continuous fluorination of ethylidene dichloride, 500 parts of ethylidene chloride and 400 parts of anhydrous stannic chloride were charged into a mild steel autoclave, and the mixture heated to 70 C. 250 parts of anhydrous hydrogen fluoride at a constant rate of 166 parts per hour were introduced and the pressure was maintained at 65 1bs./sq. in., by continuously withdrawing the product. A yield of l-fluoro-lchloroethane and 1, l-difiuoroethane, based on ethylidene chloride used, of 37.8% and 25.1% respectively was obtained.

Example 4 840 parts of asym-tetrachloroethane. 200 parts of anhydrous hydrogen fluoride and 208 parts of anhydrous stannic chloride were charged into a mild steel autoclave. The mixture was heated to 150 C. and a gauge pressure of 200 to 230 lbs/sq. in., was employed. After 3 hours the evolution of hydrogen chloride had ceased, the heating was stopped, the pressure released and the reaction mixture was allowed to cool. Distillation of the product gave a conversion of asym-tetrachloroethane to 'l-fluoro-1,1,2-trichloroethane of 46% and to 1, l-difluoro-l, 2-dichloroethane of 5%.

Example 5 668 parts of 1,1,2-trichloroethane, 120 parts of anhydrous hydrogen fluoride, and 180 parts of anhydrous stannic chloride were charged into a mild steel autoclave. The mixture was heated to 140 C. at a gauge pressure of approximately 280 lbs/sq. in. After three hours, the heating was stopped, the pressure released, and the reaction mixture allowed to cool. Distillation of the product gave a yield to l-fluoro-1,2-dichloroethane of 33% based on 1,1,2-trichloroethane consumed. No coke or tarry byproduct was formed in the reaction.

I claim:

1. The process which comprises heating a polychlorinated ethane containing at least two chlorine atoms attached to the same carbon atom with from 1 to about 3.58 stoichiometric equivalents of anhydrous hydrogen fluoride in the presence of at least 2.5% by weight of stannic chloride based on the polychlorinated ethane at a temperature of from about 50 C. to about 150 C.

2. The process which comprises heating a polychlorinated ethane containing at least two chlorine atoms attached to the same carbon atom with from 1 to about 3.58 stoichiometric equivalents of anhydrous hydrogen fluoride in the presence of at least 2.5% by weight of stannic chloride based on the polychlorinated ethane at a temperature of from about 50 C. to about 150 C.

. and at elevated pressure.

3. The process which comprises heating a polychlorinated ethane containing at least two chlorine atoms attached to the same carbon atom with from 1 to about 3.58 stoichiometric equivalents of anhydrous hydrogen fluoride in the presence of from about 20% to about 102% by of a polychlorinated ethane, containing at least two chlorine atoms attached to the same carbon atom, and at least 2.5% by weight of stannic chloride based on the polychlorinated ethane until from 1 to about 3.58 stoichiometric equivalents of hydrogen fluoride have been added to the charge, said charge being maintained at a temperature of from about 50 C. to about 150 C. and at an elevated pressure, and continuously withdrawing a monofiuorinated product from the charge.

5. The process which comprises continuously adding anhydrous hydrogen fluoride to a charge of a polychlorinated ethane, containing at least two chlorine atoms attached to the same carbon atom, and from about 20% to about 102% by weight of stannic chloride based on the polychlorinated ethane until from 1 to about 3.58 stoichiometric equivalents of hydrogen fluoride have been added to the charge, said charge being manitained at a temperature of from about 50 C. to about 150 C. and at elevated pressure, and continuously withdrawing a monofluorinated product from the charge.

6. The process for the production of l-fluoro l-chloro-ethane which comprises heating ethylidene dichloride with from 1 to about 3.58

'stoichiometric equivalents of anhydrous hydrogen fluoride in the presence of at least 2.5% by weight of stannic chloride based on the ethylidene dichloride at a temperature of from about 50 C. to about 150 C. and at elevated pressure.

7. The processior the production of l-fiuoro l-chloro-ethane which comprises heating ethylon the ethylidene dichloride at a temperature of from about C. to about 150 C. and at elevated asyrn. tetrachloroethane with from 1 to about 3.58 stoichiometric equivalents of anhydrous hydrogen fluoride in the presence of at least 2.5% by weight of stannic chloride based on the asym. tetrachloroethane at a temperature of from about 50 C. to about C. and at elevated pressure.

9. The process for the production of l-fluoro- 1,2-dichloroethane which comprises heating 1,1,2- trichloroethane with from 1 to about 3.58 stoichiometric equivalents of anhydrous hydrogen fluoride in the presence of at least 2.5% by weight of stannic chloride based on the 1,1,2-trichloroethane at a temperature of from about 50 C. to about 150 C. at elevated pressure.

WILLIAM BASIL WHALLEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS- Number Name Date 2,005,710 Daudt et al June 18, 1935 FOREIGN PATENTS Number Country i Date 670,130 Germany Jan. 12, 1939 OTHER REFERENCES I-Ienne et al., Jour. Am. Chem. Soc., vol. '58, 404-6 (1936). 

